Light emitting device

ABSTRACT

Provided is a light emitting device with effectively improved color rendering properties. A light emitting device  1  includes: a light source  2  that emits light having the maximum intensity at a predetermined wavelength; a first phosphor (yellow phosphor)  51  that absorbs the light emitted by the light source  2  and outputs fluorescent light having the maximum intensity at a first wavelength which is longer than the predetermined wavelength; and a second phosphor (red phosphor)  52  that absorbs the light emitted by the light source  2  and outputs fluorescent light having the maximum intensity at a second wavelength which is longer than the first wavelength. An absolute value of wavelength dependency of an optical absorption rate of the second phosphor  52  at the first wavelength is set to not more than 0.6%/nm. Accordingly, the color rendering properties of the light emitted by the light emitting device  1  can be effectively improved.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/122,683 filed on Nov. 27, 2013, which is a National Phase filingunder 35 U.S.C. §371 of International Application No. PCT/JP2012/058861filed on Apr. 2, 2012, and which claims priority to Japanese PatentApplication No. 2011-121811 filed on May 31, 2011.

TECHNICAL FIELD

The present invention relates to a light emitting device provided with alight source and a phosphor that absorbs light emitted by the lightsource and outputs fluorescent light.

BACKGROUND ART

A light emitting device using an element represented by an LED (LightEmitting Diode) and the like has recently been used in a variety ofapplications since having advantages of low power consumption, a smallsize, high luminance and a long lifetime. In particular, attention isbeing focused on its application to an illumination device that isreplaced for an incandescent lamp and the like with large powerconsumption.

Generally, making the element such as the LED emit white light isdifficult, differently from the incandescent lamp. For this reason, thelight emitting device using such an element further includes a phosphor,which absorbs light emitted by the element and outputs fluorescentlight, and the device emits white light by mixture of the light emittedby the element and the light outputted by the phosphor. For example,there has already been widespread a light emitting device including anLED that emits blue light and a phosphor that outputs yellow fluorescentlight.

However, the white (mixed color of blue and yellow) light emitted by theabove light emitting device has a smaller red component (is cool-colorlight) as compared with the white (white generated by radiation andclose to natural light) light outputted by the incandescent lamp and thelike. For this reason, it is difficult to make such a light emittingdevice emit white light which is warm-color light required for examplefor a household illumination device and the like.

Therefore, for example in Patent Document 1, there is provided a lightemitting device where an LED that emits blue light and a phosphor thatoutputs yellow fluorescent light are further added with a phosphor thatoutputs red fluorescent light, to emit white light replenished with ared component.

PRIOR ART DOCUMENT Patent Document

-   Patent Document 1: Japanese Patent Application Laid-Open No.    2006-124501

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

As thus described, color rendering properties of light emitted by thelight emitting device can be improved by further providing the phosphorcapable of outputting fluorescent light of a color in short in the lightemitting device. However, such simple mixture of colors by justreplenishing a color component in short cannot sufficiently improvecolor rendering properties, which is thus problematic.

In view of the above problem, it is an object of the present inventionto provide a light emitting device with effectively improved colorrendering properties.

Means for Solving the Problem

In order to achieve the above object, the present invention provides alight emitting device including: a light source that emits light havingthe maximum intensity at a predetermined wavelength;

a first phosphor that absorbs the light emitted by the light source andoutputs fluorescent light having the maximum intensity at a firstwavelength which is longer than the predetermined wavelength; and

a second phosphor that absorbs the light emitted by the light source andoutputs fluorescent light having the maximum intensity at a secondwavelength which is longer than the first wavelength, wherein

an absolute value of wavelength dependency of an optical absorption rateof the second phosphor at the first wavelength is not more than 0.6%/nm.

For example, the wavelength dependency of the optical absorption rate ofthe second phosphor at the first wavelength can be obtained as aninclination of the optical absorption rate with respect to thewavelength.

Further, in the light emitting device having the above characteristics,it is preferable that the predetermined wavelength be not shorter than420 nm and not longer than 480 nm,

the first wavelength be not shorter than 500 nm and not longer than 580nm, and

the second wavelength be not shorter than 600 nm and not longer than 680nm.

Further, in the light emitting device having the above characteristics,it is preferable that the absolute value of the wavelength dependency ofthe optical absorption rate of the second phosphor at the firstwavelength be not more than 0.4%/nm.

Further, in the light emitting device having the above characteristics,it is preferable that, when a shorter wavelength is represented by λsand a longer wavelength is represented by λl out of wavelengths at whichintensities are one-half of the intensity at the first wavelength as tothe fluorescent light outputted by the first phosphor, and

an optical absorption rate of the second phosphor at a certainwavelength λ is represented by RAbs(λ),

RAbs(λl)/RAbs(λs) be larger than 0.21.

Further, in the light emitting device having the above characteristics,it is preferable that RAbs(λl)/RAbs(λs) be larger than 0.24.

Further, in the light emitting device having the above characteristics,it is preferable that the first phosphor be a YAG phosphor added with Ceas an activator, and the second phosphor be a CaAlSiN₃ phosphor addedwith Eu as an activator.

Further, in the light emitting device having the above characteristics,it is preferable that a matrix of the second phosphor be represented bya composition formula of (Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b).

Further, in the light emitting device having the above characteristics,it is preferable that a value of b in the composition formula of(Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b) of the matrix of the secondphosphor be not smaller than 0 and not larger than 0.4.

Effect of the Invention

As described later, concentrated studies by the inventors of the presentinvention have found that the color rendering properties of the lightemitting device can be effectively improved by making small thewavelength dependency of the optical absorption rate of the secondphosphor in a fluorescent light region of the first phosphor. The lightemitting device having the above characteristics has color renderingproperties effectively improved by making small the wavelengthdependency of the optical absorption rate of the second phosphor in thefluorescent light region of the first phosphor.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view showing an example of a schematic structureof a light emitting device according to an embodiment of the presentinvention.

FIG. 2 is a graph showing properties of a yellow phosphor obtained by acommon manufacturing example.

FIG. 3A and FIG. 3B comprise graphs showing properties of a red phosphorobtained by a first manufacturing example.

FIG. 4A and FIG. 4B comprise graphs showing properties of a red phosphorobtained by a second manufacturing example.

FIG. 5A and FIG. 5B comprise graphs showing properties of a red phosphorobtained by a first comparative manufacturing example.

FIG. 6A and FIG. 6B comprise graphs showing properties of a red phosphorobtained by a second comparative manufacturing example.

FIG. 7 is a table explaining Examples 1 to 4 and Comparative Examples 1to 4.

FIG. 8A through FIG. 8D comprise graphs showing properties of lightemitting devices in Examples 1 to 4.

FIG. 9A through FIG. 9D comprise graphs showing properties of lightemitting devices in Comparative Examples 1 to 4.

FIG. 10A and FIG. 10B comprise tables showing, as comparing, theproperties of the light emitting devices in Examples 1 to 4 and theproperties of the light emitting devices in Comparative Examples 1 to 4.

FIG. 11 is a graph showing, as comparing, properties of the redphosphors obtained respectively by the first manufacturing example, thesecond manufacturing example, the first comparative manufacturingexample and the second comparative manufacturing example.

FIG. 12A and FIG. 12B comprise graphs showing the relation betweenwavelength dependency of an optical absorption rate of the red phosphorand color rendering properties.

FIG. 13A and FIG. 13B comprise graphs showing the relation between aratio of optical absorption rates (RAbs(λl)/RAbs(λs)) and the colorrendering properties of the red phosphor.

FIG. 14 is a graph showing properties of a red phosphor obtained by athird comparative manufacturing example.

FIG. 15A and FIG. 15B comprise graphs showing the relation between avalue of b and the properties of the red phosphor.

MODE FOR CARRYING OUT THE INVENTION Schematic Structural Example ofLight Emitting Device

First, an example of a schematic structure of a light emitting deviceaccording to an embodiment of the present invention will be describedwith reference to FIG. 1. FIG. 1 is a sectional view showing an exampleof a schematic structure of a light emitting device according to anembodiment of the present invention.

As shown in FIG. 1, a light emitting device 1 includes: a light source 2made up of an LED; a substrate 3 whose upper surface is provided withthe light source 2; a frame 4 which is provided on the upper surface ofthe substrate 3 and whose inside is arranged with the light source 2; amold portion 5 which fills the inside of the frame 4; and conductiveadhesive 6 and wire 7 which electrically connect between the lightsource 2 and the substrate 3.

The light source 2 is provided with a semiconductor layer 21 including,for example, InGaN as an active layer, and a p-side electrode 22 and ann-side electrode 23 which hold the semiconductor device therebetween.The substrate 3 is made up of, for example, a print substrate, and ap-electrode portion 31 and an n-electrode portion 32 are formed from theupper surface and the lower surface thereof. The p-side electrode 22 andthe p-electrode portion 31 are attached and electrically connected toeach other by the adhesive 6. Further, the n-side electrode 23 and then-electrode portion 32 are electrically connected to each other by thewire 7. As thus described, the inside of the frame 4 is filled with themold portion 5 in the state where the substrate 3 and the light source 2are electrically connected to each other, to seal the light source 2.

The light source 2 is excited by electric power supplied through thep-electrode portion 31 and the adhesive 6 or the n-electrode portion 32and the wire 7, and emits blue light (light with the maximum intensityat a wavelength, namely a peak wavelength, being not shorter than 420 nmand not longer than 480 nm, and the same shall apply hereinafter). Ayellow phosphor 51 absorbs the blue light emitted by the light source 2and outputs yellow fluorescent light (light with a peak wavelength ofnot shorter than 500 nm and not longer than 580 nm, and the same shallapply hereinafter). A red phosphor 52 absorbs the blue light emitted bythe light source 2 and outputs red fluorescent light (light with a peakwavelength of not shorter than 600 nm and not longer than 680 nm, andthe same shall apply hereinafter).

The light source 2 is not restricted to the aforementioned LED, but avariety of known elements that can emit blue light, such as an LD (LaserDiode) and an inorganic EL (electroluminescence) element, areapplicable. For example, an LED as a commercial product (e.g., oneproduced by Cree, Inc.) is applicable to the aforementioned light source2.

The mold portion 5 is provided with: a translucent resin (e.g. siliconresin, epoxy resin, etc.) 50; a phosphor (hereinafter referred to as ayellow phosphor) 51 that is dispersed in the translucent resin 50,absorbs the light emitted by the light source 2 (or excited by thelight), and outputs yellow fluorescent light; and a phosphor(hereinafter referred to as a red phosphor) 52 that is dispersed in thetranslucent resin 50, absorbs the light emitted by the light source 2(or excited by the light), and outputs red fluorescent light. Any methodmay be used as a method for dispersing the yellow phosphor 51 and thered phosphor 52 into the translucent resin 50, and a known method isapplicable.

A mixed ratio of the translucent resin 50, the yellow phosphor 51 andthe red phosphor 52 is appropriately selectable in accordance with acolor of light intended to be emitted (e.g. white which is a warm colorclose to natural light like one emitted by the incandescent lamp).Specifically, for example, the mixed ratio may be decided such that amass ratio of the translucent resin 50 with respect to the yellowphosphor 51 and the red phosphor 52 (mass of translucent resin 50/totalmass of yellow phosphor 51 and red phosphor 52) is within a range of notless than 5 and not more than 50. Further, for example, the mixed ratiomay be decided such that a mass ratio of the red phosphor 52 withrespect to the yellow phosphor 51 (mass ratio of red phosphor 52/yellowphosphor 51) is within a range of not less than 0.1 and not more than 1.

It is to be noted that the light emitting device 1 according to theembodiment of the present invention described above is merely anexample, and the present invention is naturally applicable to a lightemitting device with a different structure. However, the aforementionedlight emitting device 1 will be assumed hereinafter so long as noparticular remark is made for the sake of embodying descriptions.

<<Manufacturing Method for Yellow Phosphor and Red Phosphor>>

An example of a manufacturing method for the yellow phosphor and the redphosphor will be described in detail with reference to the drawings.However, part of the examples of the manufacturing method mentionedhereinafter (especially an example of the manufacturing method by whichthe yellow phosphor and the red phosphor provided in Examples of thelight emitting device can be manufactured) is merely an example of themanufacturing method applicable to the light emitting device of thepresent invention, and the light emitting device of the presentinvention is not restricted to a light emitting device obtained by thatexample of the manufacturing method.

<Manufacturing Method for Yellow Phosphor (Provided in Examples andComparative Examples of the Light Emitting Device)>

For example, a YAG phosphor (a phosphor containing one with acomposition formula of Y₃Al₅O₁₂ (including substances obtained byreplacing part or all of Y, Al and O with predetermined elements), andthe same shall apply hereinafter) added with Ce as an activator can beused for the yellow phosphor. Specifically, for example, a phosphor witha composition formula of Y_(3-a)Ce_(a)Al₅O₁₂ can be used for the yellowphosphor. The yellow phosphor is obtained for example by a commonmanufacturing example which will be described hereinafter. It is to benoted that the common manufacturing example which will be describedhereinafter is capable of manufacturing the yellow phosphor provided ineach of undermentioned Examples and Comparative Examples of the lightemitting device.

Common Manufacturing Example

The common manufacturing example is to manufacture a yellow phosphorwith a composition formula of Y_(3-a)Ce_(a)Al₅O₁₂, where a=0.065. In thecommon manufacturing example, first, 86.1 mass % of a yttrium oxidepower, 2.1 mass % of a cerium oxide powder, 11.8 mass % of an aluminumoxide powder and predetermined amounts of calcium fluoride and ammoniumhydrogen phosphate as a flux are weighted, and then mixed by a tumblingball mill formed using an agate-made ball and a nylon pot. Next, aquartz crucible is filled with the obtained mixture and in a reducingatmosphere made up of 95 vol % of nitrogen and 5 vol % of hydrogen, itis held at 1550° C. for 10 hours. Then, the obtained burned substance isground by an agate-made mortar, to obtain a powdery yellow phosphor.

Properties of the yellow phosphor obtained by the common manufacturingexample will be described with reference to FIG. 2. FIG. 2 is a graphshowing properties of the yellow phosphor obtained by the commonmanufacturing example. The graph shown in FIG. 2 represents afluorescence spectrum in the case of irradiating the yellow phosphorwith light (blue light) having a peak wavelength of 450 nm, where ahorizontal axis indicates a wavelength (nm) and a vertical axisindicates an intensity (normalized by an arbitrary intensity).

As shown in FIG. 2, the yellow phosphor obtained by the commonmanufacturing example absorbs blue light and outputs yellow fluorescentlight with a peak wavelength of 558 nm and a half width of 115 nm. Whena shorter wavelength is represented by λs (the same shall applyhereinafter) and a longer wavelength is represented by λl (the sameshall apply hereinafter) out of wavelengths at which intensities areone-half of the intensity at the peak wavelength as to the fluorescentlight outputted by the yellow phosphor, λs=515 nm and λl=630 nm.Further, chromaticity coordinates of a fluorescence spectrum of theyellow phosphor are: (x, y)=(0.447, 0.534).

<Manufacturing Method for Red Phosphor (Provided in Examples of LightEmitting Device)>

For example, a CaAlSiN₃ phosphor (a phosphor containing one with acomposition formula of CaAlSiN₃ (including substances obtained byreplacing part or all of Ca, Al, Si and N with predetermined elements),and the same shall apply hereinafter) added with Eu as the activator canbe used for the red phosphor. Specifically, for example, a phosphor witha composition formula of (Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b) can beused for the red phosphor. The red phosphor is obtained for example by afirst manufacturing example and a second manufacturing example whichwill be described hereinafter. It is to be noted that the firstmanufacturing example and the second manufacturing example which will bedescribed hereinafter are capable of manufacturing the red phosphorprovided in undermentioned Examples of the light emitting device.

First Manufacturing Example

The first manufacturing example is to manufacture a red phosphor of(Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b), where b=0 and c(1−b)=0.008.

First, 29.7 mass % of an aluminum nitride power, 33.9 mass % of anα-type silicon nitride powder, 35.5 mass % of a calcium nitride powderand 1.0 mass % of a europium nitride powder are weighted, and then mixedusing a mortar and a pestle made of a silicon nitride burned substancefor not shorter than 10 minutes. In addition, this europium nitride isobtained by performing nitridation synthesis on metal europium inammonia.

Next, the obtained powder aggregate is naturally dropped into a pot madeof boron nitride having a size with a diameter of 20 mm and a height of20 mm, to fill the pot. It is to be noted that the processes up to here(weighing, mixing and shaping of the powder materials) are performed ina globe box for holding a nitrogen atmosphere with moisture of not morethan 1 ppm and oxygen of not more than 1 ppm.

The pot filled with the powder aggregate is heated in a nitrogenatmosphere of 99.999 vol % and 1 MPa by use of a graphite-resistanceheating electric furnace. At this time, the temperature is increased upto 1800° C. at a programming rate of 500° C. per hour, and is furtherheld at 1800° C. for two hours. Then, the obtained burned substance isground by an agate-made mortar, to obtain a powdery red phosphor.

The powder of the red phosphor obtained as described above has a crystalstructure where a CaAlSiN₃ phase with a structure of CaAlSiN₃ crystal isa principal phase (phase existing in the largest amount, specifically aphase existing in an amount of not smaller than 50 mass %, for example,and the same shall apply hereinafter). It is to be noted that thecrystal structure was confirmed by powder X-ray diffraction (XRD)measurement using a Cu-Kα ray. Further, when the red phosphor powder wasirradiated with light with a wavelength of 450 nm, output of redfluorescent light was confirmed.

Fluorescent properties of the red phosphor obtained by the firstmanufacturing example will be described with reference to FIG. 3. FIG. 3includes graphs showing properties of the red phosphor obtained by thefirst manufacturing example. The graph shown in FIG. 3A represents afluorescence spectrum in the case of irradiating the red phosphor withlight (blue light) having a peak wavelength of 450 nm, where ahorizontal axis indicates a wavelength (nm) and a vertical axisindicates an intensity (normalized by an arbitrary intensity). Further,the graph shown in FIG. 3B is a graph showing an optical absorptionspectrum of the red phosphor, where a horizontal axis indicates awavelength (nm) and a vertical axis indicates an optical absorption rate(%). It is to be noted that the graph shown in FIG. 3B is obtained suchthat a measurement cell having a depth of 5 mm and a diameter of 15 mmis filled with the powdery red phosphor, obtained by the firstmanufacturing example, as densely as possible by natural dropping andtapping, and this cell filled with the red phosphor is measured by ameasurement system provided with a spectro-photometer and an integratingsphere.

As shown in FIG. 3A, the red phosphor obtained by the firstmanufacturing example absorbs blue light and outputs red fluorescentlight with a peak wavelength of 648 nm and a half width of 89 nm.Further, chromaticity coordinates of a fluorescence spectrum of the redphosphor are: (x, y)=(0.657, 0.340).

Moreover, as for the graph shown in FIG. 3B, an absolute value ofwavelength dependency of an optical absorption rate (inclination of anoptical absorption rate with respect to a wavelength, and the same shallapply hereinafter) of the red phosphor at a peak wavelength (558 nm) ofthe fluorescent light outputted by the yellow phosphor obtained by theaforementioned common manufacturing example is obtained to be 0.38%/nm.Furthermore, as for the graph shown in FIG. 3B, a ratio is obtained bydividing an optical absorption rate RAbs(λl) of the red phosphor at theaforementioned wavelength λl by an optical absorption rate RAbs(λs) ofthe red phosphor at the aforementioned wavelength λs, to beRAbs(λl)/RAbs(λs)=0.25.

Second Manufacturing Example

The second manufacturing example is to manufacture a red phosphor of(Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b), where b=0.33 and c(1−b)=0.023.

First, 14.3 mass % of an aluminum nitride power, 8.9 mass % of analuminum oxide powder, 48.9 mass % of an a-type silicon nitride powder,25.0 mass % of a calcium nitride powder, and 3.0 mass % of a europiumoxide powder are weighted, and then mixed using a mortar and a pestlemade of a silicon nitride burned substance for not shorter than 10minutes.

Next, the obtained powder aggregate is naturally dropped into a pot madeof boron nitride having a size with a diameter of 20 mm and a height of20 mm, to fill the pot. It is to be noted that the processes up to here(weighing, mixing and shaping of the powder materials) are performed ina globe box for holding a nitrogen atmosphere with moisture of not morethan 1 ppm and oxygen of not more than 1 ppm.

The pot filled with the powder aggregate is heated in a nitrogenatmosphere of 99.999 vol % and 1 MPa by use of a graphite-resistanceheating electric furnace. At this time, the temperature is increased upto 1800° C. at a programming rate of 500° C. per hour, and is furtherheld at 1800° C. for two hours. Then, the obtained burned substance isground by an agate-made mortar, to obtain a powdery red phosphor.

The powder of the red phosphor obtained as described above has a crystalstructure where a CaAlSiN₃ phase with a structure of CaAlSiN₃ crystal isa principal phase. It is to be noted that the crystal structure wasconfirmed by powder X-ray diffraction (XRD) measurement using a Cu-Kαray. Further, when the red phosphor powder was irradiated with lightwith a wavelength of 450 nm, output of red fluorescent light wasconfirmed.

Fluorescent properties of the red phosphor obtained by the secondmanufacturing example will be described with reference to FIG. 4. FIG. 4includes graphs showing properties of the red phosphor obtained by thesecond manufacturing example. The graph shown in FIG. 4A represents afluorescence spectrum in the case of irradiating the red phosphor withlight (blue light) having a peak wavelength of 450 nm, where ahorizontal axis indicates a wavelength (nm) and a vertical axisindicates an intensity (normalized by an arbitrary intensity). Further,the graph shown in FIG. 4B is a graph showing an optical absorptionspectrum of the red phosphor, where a horizontal axis indicates awavelength (nm) and a vertical axis indicates an optical absorption rate(%). It is to be noted that the graph shown in FIG. 4B is obtained suchthat a measurement cell having a depth of 5 mm and a diameter of 15 mmis filled with the powdery red phosphor, obtained by the secondmanufacturing example, as densely as possible by natural dropping andtapping, and this cell filled with the red phosphor is measured by ameasurement system provided with a spectro-photometer and an integratingsphere.

As shown in FIG. 4A, the red phosphor obtained by the secondmanufacturing example absorbs blue light and outputs red fluorescentlight with a peak wavelength of 643 nm and a half width of 100 nm.Further, chromaticity coordinates of a fluorescence spectrum of the redphosphor are: (x, y)=(0.628, 0.369).

Moreover, as for the graph shown in FIG. 4B, an absolute value ofwavelength dependency of an optical absorption rate of the red phosphorat a peak wavelength (558 nm) of the fluorescent light outputted by theyellow phosphor obtained by the aforementioned common manufacturingexample is obtained, to be 0.43%/nm. Furthermore, as for the graph shownin FIG. 4B, a ratio is obtained by dividing an optical absorption rateRAbs(λl) of the red phosphor at the aforementioned wavelength λl by anoptical absorption rate RAbs(λs) of the red phosphor at theaforementioned wavelength λs, to be RAbs(λl)/RAbs(λs)=0.24.

<Manufacturing Method for Red Phosphor (Provided in Comparative Examplesof Light Emitting Device)>

For example, a Ba₂Si₅N₈ phosphor added with Eu as the activator, anSr₂Si₅N₈ phosphor added with Eu as the activator can also be used forthe red phosphor. These red phosphors are obtained for example by afirst comparative manufacturing example and a second comparativemanufacturing example which will be described hereinafter. It is to benoted that the first comparative manufacturing example and the secondcomparative manufacturing example which will be described hereinafterare capable of manufacturing the red phosphor provided in theundermentioned comparative example of the light emitting device.

First Comparative Manufacturing Example

The first comparative manufacturing example is to manufacture a redphosphor made up of the Ba₂Si₅N₈ phosphor added with Eu as theactivator.

First, 44.1 mass % of an α-type silicon nitride powder, 55.5 mass % ofbarium nitride powder and 0.4 mass % of a europium nitride powder areweighted, and then mixed using a mortar and a pestle made of a siliconnitride burned substance for not shorter than 10 minutes. In addition,this europium nitride is obtained by performing nitridation synthesis onmetal europium in ammonia.

Next, the obtained powder aggregate is naturally dropped into a pot madeof boron nitride having a size with a diameter of 20 mm and a height of20 mm, to fill the pot. It is to be noted that the processes up to here(weighing, mixing and shaping of the powder materials) are performed ina globe box for holding a nitrogen atmosphere with moisture of not morethan 1 ppm and oxygen of not more than 1 ppm.

The pot filled with the powder aggregate is heated in a nitrogenatmosphere of 99.999 vol % and 1 MPa by use of a graphite-resistanceheating electric furnace. At this time, the temperature is increased upto 1600° C. at a programming rate of 500° C. per hour, and is furtherheld at 1600° C. for two hours. Then, the obtained burned substance isground by an agate-made mortar, to obtain a powdery red phosphor.

The powder of the red phosphor obtained as described above has a crystalstructure where a Ba₂Si₅N₈ phase with a structure of Ba₂Si₅N₈ crystal isa principal phase. It is to be noted that the crystal structure wasconfirmed by powder X-ray diffraction (XRD) measurement using a Cu-Kαray. Further, when the red phosphor powder was irradiated with lightwith a wavelength of 365 nm, output of red fluorescent light wasconfirmed.

Fluorescent properties of the red phosphor obtained by the firstcomparative manufacturing example will be described with reference toFIG. 5. FIG. 5 includes graphs showing properties of the red phosphorobtained by the first comparative manufacturing example. The graph shownin FIG. 5A represents a fluorescence spectrum in the case of irradiatingthe red phosphor with light (blue light) having a peak wavelength of 450nm, where a horizontal axis indicates a wavelength (nm) and a verticalaxis indicates an intensity (normalized by an arbitrary intensity).Further, the graph shown in FIG. 5B is a graph showing an opticalabsorption spectrum of the red phosphor, where a horizontal axisindicates a wavelength (nm) and a vertical axis indicates an opticalabsorption rate (%). It is to be noted that the graph shown in FIG. 5Bis obtained such that a measurement cell having a depth of 5 mm and adiameter of 15 mm is filled with the powdery red phosphor, obtained bythe first comparative manufacturing example, as densely as possible bynatural dropping and tapping, and this cell filled with the red phosphoris measured by a measurement system provided with a spectro-photometerand an integrating sphere.

As shown in FIG. 5A, the red phosphor obtained by the first comparativemanufacturing example absorbs blue light and outputs red fluorescentlight with a peak wavelength of 650 nm and a half width of 107 nm.Further, chromaticity coordinates of a fluorescence spectrum of the redphosphor are: (x, y)=(0.663, 0.337).

Moreover, as for the graph shown in FIG. 5B, an absolute value ofwavelength dependency of an optical absorption rate of the red phosphorat a peak wavelength (558 nm) of the fluorescent light outputted by theyellow phosphor obtained by the aforementioned common manufacturingexample is obtained, to be 0.75%/nm. Furthermore, as for the graph shownin FIG. 5B, a ratio is obtained by dividing an optical absorption rateRAbs(λl) of the red phosphor at the aforementioned wavelength λl by anoptical absorption rate RAbs(λs) of the red phosphor at theaforementioned wavelength λs, to be RAbs(λl)/RAbs(λs)=0.18.

Second Comparative Manufacturing Example

The second comparative manufacturing example is to manufacture a redphosphor made up of the Sr₂Si₅N₈ phosphor added with Eu as theactivator.

First, 54.3 mass % of an a-type silicon nitride powder, 45.1 mass % ofstrontium nitride powder and 0.6 mass % of a europium nitride powder areweighted, and then mixed using a mortar and a pestle made of a siliconnitride burned substance for not shorter than 10 minutes. In addition,this europium nitride is one obtained by performing nitridationsynthesis on metal europium in ammonia.

Next, the obtained powder aggregate is naturally dropped into a pot madeof boron nitride having a size with a diameter of 20 mm and a height of20 mm, to fill the pot. It is to be noted that the processes up to here(weighing, mixing and shaping of the powder materials) are performed ina globe box for holding a nitrogen atmosphere with moisture of not morethan 1 ppm and oxygen of not more than 1 ppm.

The pot filled with the powder aggregate is heated in a nitrogenatmosphere of 99.999 vol % and 1 MPa by use of a graphite-resistanceheating electric furnace. At this time, the temperature is increased upto 1600° C. at a programming rate of 500° C. per hour, and is furtherheld at 1600° C. for two hours. Then, the obtained burned substance isground by an agate-made mortar, to obtain a powdery red phosphor.

The powder of the red phosphor obtained as described above has a crystalstructure where a Sr₂Si₅N₈ phase with a structure of Sr₂Si₅N₈ crystal isa principal phase. It is to be noted that the crystal structure wasconfirmed by powder X-ray diffraction (XRD) measurement using a Cu-Kαray. Further, when the red phosphor powder was irradiated with lightwith a wavelength of 365 nm, output of red fluorescent light wasconfirmed.

Fluorescent properties of the red phosphor obtained by the secondcomparative manufacturing example will be described with reference toFIG. 6. FIG. 6 includes graphs showing properties of the red phosphorobtained by the second comparative manufacturing example. The graphshown in FIG. 6A represents a fluorescence spectrum in the case ofirradiating the red phosphor with light (blue light) having a peakwavelength of 450 nm, where a horizontal axis indicates a wavelength(nm) and a vertical axis indicates an intensity (normalized by anarbitrary intensity). Further, the graph shown in FIG. 6B is a graphshowing an optical absorption spectrum of the red phosphor, where ahorizontal axis indicates a wavelength (nm) and a vertical axisindicates an optical absorption rate (%). It is to be noted that thegraph shown in FIG. 6B is obtained such that a measurement cell having adepth of 5 mm and a diameter of 15 mm is filled with the powdery redphosphor, obtained by the second comparative manufacturing example, asdensely as possible by natural dropping and tapping, and this cellfilled with the red phosphor is measured by a measurement systemprovided with a spectro-photometer and an integrating sphere.

As shown in FIG. 6A, the red phosphor obtained by the second comparativemanufacturing example absorbs blue light and outputs red fluorescentlight with a peak wavelength of 642 nm and a half width of 106 nm.Further, chromaticity coordinates of a fluorescence spectrum of the redphosphor are: (x, y)=(0.657, 0.343).

Moreover, as for the graph shown in FIG. 6B, an absolute value ofwavelength dependency of an optical absorption rate of the red phosphorat a peak wavelength (558 nm) of the fluorescent light outputted by theyellow phosphor obtained by the aforementioned common manufacturingexample is obtained, to be 0.83%/nm. Furthermore, as for the graph shownin FIG. 6B, a ratio is obtained by dividing an optical absorption rateRAbs(λl) of the red phosphor at the aforementioned wavelength λl by anoptical absorption rate RAbs(λs) of the red phosphor at theaforementioned wavelength λs, to be RAbs(λl)/RAbs(λs)=0.17.

It should be noted that in the measurement of the optical absorptionrates of the yellow phosphor and the red phosphor described above, aswell as measurement of an optical absorption rate of a phosphordescribed later, there can for example be applied a measurement methoddescribed in “Absolute Fluorescent Quantum Efficiency of NBS PhosphorStandard Samples” [Ohkubo Kazuaki, et al., IEIJ (IlluminatingEngineering Institute of Japan) Journal, Vol. 83 No. 2, p. 87 (1999)].

Examples and Comparative Examples of Light Emitting Device

Hereinafter, Examples 1 to 4 of the light emitting device according tothe embodiment of the present invention and Comparative Examples 1 to 4of the light emitting device will be respectively mentioned, and theselight emitting devices will be described with reference to the drawings.

First, Examples 1 to 4 and Comparative Examples 1 to 4 will be describedwith reference to FIG. 7. FIG. 7 is a table explaining Examples 1 to 4and Comparative Examples 1 to 4.

As shown in FIG. 7, the light emitting devices of Examples 1 and 3 eachinclude the red phosphor obtained by the first manufacturing example,and the light emitting devices of Examples 2 and 4 each include the redphosphor obtained by the second manufacturing example. On the otherhand, the light emitting devices of Comparative Examples 1 and 3 eachinclude the red phosphor obtained by the first comparative manufacturingexample, and the light emitting devices of Comparative Examples 2 and 4each include the red phosphor obtained by the second comparativemanufacturing example. Further, as shown in FIG. 7, the light emittingdevices of Examples 1 and 2 each include a light source whose emittedlight has a peak wavelength of 450 nm, and the light emitting devices ofExamples 3 and 4 each include a light source whose emitted light has apeak wavelength of 460 nm. On the other hand, the light emitting devicesof Comparative Examples 1 and 2 each include a light source whoseemitted light has a peak wavelength of 450 nm, and the light emittingdevices of Comparative Examples 3 and 4 each include a light sourcewhose emitted light has a peak wavelength of 460 nm. It is to be notedthat the light emitting devices of Examples 1 to 4 and ComparativeExamples 1 to 4 each include the yellow phosphor obtained by the commonmanufacturing example. Moreover, the light emitting devices of Examples1 to 4 and Comparative Examples 1 to 4 each include a similar lightsource (e.g., product name: EZR, produced by Cree, Inc.) and a similartranslucent resin (e.g., product name: KER2500, produced by Shin-EtsuChemical Co., Ltd.).

Further, the light emitting devices of Examples 1 to 4 and ComparativeExamples 1 to 4 are each adjusted such that a color of emitted light isan incandescent color (e.g., such that chromaticity coordinates are: (x,y)=(0.451 to 0.452, 0.408 to 0.409)). Specifically, a mass ratio of thetranslucent resin constituting the mold portion to the yellow phosphorand the red phosphor and a mass ratio of the red phosphor to the yellowphosphor are adjusted in each of the light emitting devices.

Next, properties of the light emitting devices of Examples 1 to 4 andComparative Examples 1 to 4 will be described with reference to FIGS. 8to 10. FIG. 8 includes graphs showing properties of the light emittingdevices in Examples 1 to 4. Further, FIG. 9 includes graphs showingproperties of the light emitting devices in Comparative Examples 1 to 4.Moreover, FIG. 10 includes tables showing, as comparing, the propertiesof the light emitting devices in Examples 1 to 4 and the properties ofthe light emitting devices in Comparative Examples 1 to 4.

FIG. 8A is a graph showing an emission spectrum of the light emittingdevice of Example 1, FIG. 8B is a graph showing an emission spectrum ofthe light emitting device of Example 2, FIG. 8C is a graph showing anemission spectrum of the light emitting device of Example 3, and FIG. 8Dis a graph showing an emission spectrum of the light emitting device ofExample 4. Further, in each of the graphs of FIGS. 8A to 8D, ahorizontal axis indicates a wavelength (nm) and a vertical axisindicates an intensity (normalized by an arbitrary intensity).

FIG. 9A is a graph showing an emission spectrum of the light emittingdevice of Comparative Example 1, FIG. 9B is a graph showing an emissionspectrum of the light emitting device of Comparative Example 2, FIG. 9Cis a graph showing an emission spectrum of the light emitting device ofComparative Example 3, and FIG. 9D is a graph showing an emissionspectrum of the light emitting device of Comparative Example 4. Further,in each of the graphs of FIGS. 9A to 9D, a horizontal axis indicates awavelength (nm) and a vertical axis indicates an intensity (normalizedby an arbitrary intensity).

Tables shown in FIG. 10 represent properties obtained from the graphsshown in FIGS. 8 and 9. FIG. 10A is a table showing, as comparing, theproperties of the light emitting devices of Examples 1 and 2 where thelight source has a peak wavelength of 450 nm, and the properties of thelight emitting devices of Comparative Examples 1 and 2 where the lightsource has a peak wavelength of 450 nm as well. Meanwhile, FIG. 10B is atable showing, as comparing, the properties of the light emittingdevices of Examples 3 and 4 where the light source has a peak wavelengthof 460 nm, and the properties of the light emitting devices ofComparative Examples 3 and 4 where the light source has a peakwavelength of 460 nm as well.

Each of Ra and R9 in the tables shown in FIG. 10 is a value ofevaluation of color rendering properties. Ra is a general colorrendering index obtained by averaging values of evaluation of colorrendering properties of predetermined plurality of colors, and R9 is aspecial color rendering index showing a value of evaluation of red-colorrendering properties. The larger the values of Ra and R9, the highercolor rendering properties the values show that the light emittingdevice has.

Further, TCP, Duv, x and y in the tables shown in FIG. 10 representcolors of light emitted by the light emitting device. As describedabove, x and y are values showing chromaticity coordinates. TCP is avalue showing a correlated color temperature (color temperature obtainedby regarding object light as light on a black body radiation locus). Duvis a value showing a deviation between the object light and the blackbody radiation locus. As shown in FIG. 10, a color of light emitted fromeach of the light emitting devices of Examples 1 to 4 and ComparativeExamples 1 to 4 is the Incandescent color.

As shown in FIG. 10A, Ra and R9 in the light emitting devices ofExamples 1 and 2 are large as compared with those in the light emittingdevices of Comparative Examples 1 and 2. That is, the light emittingdevices of Examples 1 and 2 have higher color rendering properties andespecially higher red-color rendering properties than the light emittingdevices of Comparative Examples 1 and 2. Further, as shown in FIG. 10B,Ra and R9 in the light emitting devices of Examples 3 and 4 are large ascompared with those in the light emitting devices of ComparativeExamples 3 and 4. That is, the light emitting devices of Examples 3 and4 have higher color rendering properties and especially higher red-colorrendering properties than the light emitting devices of ComparativeExamples 3 and 4.

For this reason, it is possible to make the light emitting devices ofExamples 1 to 4 emit white light which is warm-color light required forexample for a household illumination device and the like. In particular,the color rendering properties (Ra=82.8, R9=42.8) of the light emittingdevice of Example 3 even exceed color rendering properties (Ra=81,R9=26) of a three-wavelength fluorescent tube as a mainstream of indoorfluorescent lamp.

As described above, the light emitting devices of Examples 1 to 4 havehigher color rendering properties than the light emitting devices ofComparative Examples 1 to 4. A factor of this will be described withreference to FIGS. 11 to 13. FIG. 11 is a graph showing, as comparing,properties of the red phosphors obtained respectively by the firstmanufacturing example, the second manufacturing example, the firstcomparative manufacturing example and the second comparativemanufacturing example. FIG. 12 includes graphs showing the relationbetween wavelength dependency of an optical absorption rate of the redphosphor and color rendering properties. FIG. 13 includes graphs showingthe relation between a ratio (RAbs(λl)/RAbs(λs)) of an opticalabsorption rate of the red phosphor and color rendering properties.

The graph shown in FIG. 11 represents each fluorescence spectrum in thecase of irradiating the red phosphor, obtained by each of the firstmanufacturing example, the second manufacturing example, the firstcomparative manufacturing example and the second comparativemanufacturing example, with light (blue light) having a peak wavelengthof 450 nm, where a horizontal axis indicates a wavelength (nm) and avertical axis indicates an intensity (normalized by an arbitraryintensity). FIG. 12A is a graph showing the relation between wavelengthdependency set for a horizontal axis and Ra set for a vertical axis, thewavelength dependency being that of an optical absorption rate of thered phosphor at a peak wavelength of the fluorescent light outputted bythe yellow phosphor, and FIG. 12B is a graph showing the relationbetween wavelength dependency set for a horizontal axis and R9 set for avertical axis, the wavelength dependency being that of an opticalabsorption rate of the red phosphor at a peak wavelength of thefluorescent light outputted by the yellow phosphor. Further, FIG. 13A isa graph showing the relation between RAbs(λl)/RAbs(λs) set for ahorizontal axis and Ra set for a vertical axis, and FIG. 13B is a graphshowing the relation between RAbs(λl)/RAbs(λs) set for a horizontal axisand R9 set for a vertical axis. Moreover, the graphs shown in FIGS. 12and 13 are obtained based on the properties of the light emittingdevices of Examples 1 to 4 and Comparative Examples 1 to 4 describedabove.

As shown in FIG. 11, when the fluorescence spectrums of the redphosphors obtained by the first manufacturing example and the secondmanufacturing example are compared with the fluorescence spectrums ofthe red phosphors obtained by the first comparative manufacturingexample and the second comparative manufacturing example, thefluorescence spectrums of the red phosphors obtained by the firstcomparative manufacturing example and the second comparativemanufacturing example have larger long-wavelength components than thefluorescence spectrums of the red phosphors obtained by the firstmanufacturing example and the second manufacturing example.

In the case based on general findings (e.g. the findings ofaforementioned Patent Document 1), it is considered that, the larger thelong-wavelength component of the red phosphor that is used, the more thecolor rendering properties of light emitted by the light emitting deviceare improved. That is, it is considered that color rendering propertiesof light emitted by the light emitting devices using the red phosphorsobtained by the first comparative manufacturing example and the secondcomparative manufacturing example are higher than those of the emittingdevices using the red phosphors obtained by the first manufacturingexample and the second manufacturing example.

However, as described with reference to FIG. 10, in practice, colorrendering properties of light emitted by the light emitting devicesusing the red phosphors obtained by the first manufacturing example andthe second manufacturing example are higher than those of the lightemitting devices using the red phosphors obtained by the firstcomparative manufacturing example and the second comparativemanufacturing example. This is supposed to be attributed to that thewavelength dependency of the optical absorption rate of each of the redphosphors obtained by the first manufacturing example and the secondmanufacturing example at the peak wavelength (558 nm) of the fluorescentlight outputted by the yellow phosphor is smaller than that of each ofthe red phosphors obtained by the first comparative manufacturingexample and the second comparative manufacturing example.

Specifically, for example, the wavelength dependency of the opticalabsorption rate of each of the red phosphors obtained by the firstmanufacturing example and the second manufacturing example as describedabove at the peak wavelength (558 nm) of the fluorescent light outputtedby the yellow phosphor is not more than 0.5%/nm. As opposed to this, thewavelength dependency of the optical absorption rate of each of the redphosphors obtained by the first comparative manufacturing example andthe second comparative manufacturing example at the peak wavelength (558nm) of the fluorescent light outputted by the yellow phosphor is notless than 0.7%/nm.

Moreover, in the graphs showing the optical absorption spectrums shownin FIGS. 3B to 6B, in a region where the wavelength is shorter than thevicinity of 550 nm, the optical absorption rate of each of the redphosphors obtained by the first manufacturing example and the secondmanufacturing example is smaller than the optical absorption rate ofeach of the red phosphors obtained by the first comparativemanufacturing example and the second comparative manufacturing example.On the other hand, in a region where the wavelength is longer than thevicinity of 550 nm, the optical absorption rate of each of the redphosphors obtained by the first manufacturing example and the secondmanufacturing example is larger than the optical absorption rate of eachof the red phosphors obtained by the first comparative manufacturingexample and the second comparative manufacturing example. That is, in aregion (hereinafter referred to as a fluorescent light region) includinga wavelength of fluorescent light emitted by the yellow phosphor, anoptical absorption amount (an integrated value of an optical absorptionrate in the fluorescent light region, and the same shall applyhereinafter) of each of the red phosphors obtained by the firstmanufacturing example and the second manufacturing example issubstantially the same as an optical absorption amount of each of thered phosphors obtained by the first comparative manufacturing exampleand the second comparative manufacturing example.

As described above, the color rendering properties of the light emittingdevice depend not on the optical absorption amount of the red phosphor,but on the shape of the optical absorption spectrum of the red phosphorin the fluorescent light region of the yellow phosphor. Specifically,the gentler the shape of the optical absorption spectrum (the smallerthe wavelength dependency of the optical absorption rate) of the redphosphor in the fluorescent light region of the yellow phosphor, thehigher the color rendering properties of the light emitting device.

When the optical absorption rate of the red phosphor is large in thefluorescent light region of the yellow phosphor, it is thought based ongeneral findings that the intensity of yellow light emitted to theoutside of the light emitting device decreases to cause deterioration incolor rendering properties. However, as described above, in practice,the larger the wavelength dependency of the optical absorption rate ofthe red phosphor in the fluorescent light region of the yellow phosphor(the wider the fluctuations of the optical absorption rate from a shortwavelength to a long wavelength), the lower the color renderingproperties. Therefore, the color rendering properties of the lightemitting device can be effectively improved by defining the wavelengthdependency of the optical absorption rate of the red phosphor in thefluorescent light region of the yellow phosphor to be small.

Here, specific conditions for improving the color rendering propertiesof the light emitting device will be described with reference to FIGS.12 and 13.

First, as shown in FIG. 12, Ra and R9 showing the color renderingproperties of the light emitting device abruptly increase when theabsolute value of the wavelength dependency of the optical absorptionrate of the red phosphor at a peak wavelength of the fluorescent lightemitted by the yellow phosphor becomes not more than 0.6%/nm. That is,the color rendering properties of the light emitting device can beeffectively improved by setting the absolute value of the wavelengthdependency of the optical absorption rate of the red phosphor at a peakwavelength of the fluorescent light emitted by the yellow phosphor tonot more than 0.6%/nm (preferably not more than 0.43%/nm, morepreferably not more than 0.4%/nm).

Further, as shown in FIG. 13, Ra and R9 showing the color renderingproperties of the light emitting device abruptly increase when the ratio(RAbs(λl)/RAbs(λs)) of the respective optical absorption rates of thered phosphor at the foregoing wavelengths λs and λl becomes larger than0.21. That is, the color rendering properties of the light emittingdevice can be effectively improved by making RAbs(λl)/RAbs(λs) largerthan 0.21 (more preferably larger than 0.24).

<<Optimization of Red Phosphor>>

As shown in FIG. 10, the color rendering properties (Ra and R9) arehigher in Examples 1 and 3 where the red phosphor obtained by the firstmanufacturing example is provided than in Examples 2 and 4 where the redphosphor obtained by the second manufacturing example is provided. For,as described above, this is attributed to that the wavelength dependencyof the optical absorption rate of the red phosphor obtained by the firstmanufacturing example is smaller than that of the red phosphor obtainedby the second manufacturing example. Hereinafter, a manufacturing methodfor a red phosphor whose optical absorption rate has small wavelengthdependency (i.e., optimization of the red phosphor) will be describedwith reference to the drawings.

Third Comparative Manufacturing Example

First, a third comparative manufacturing example will be described. Thethird comparative manufacturing example is to manufacture a red phosphorof (Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b), where b=0.45 andc(1−b)=0.023.

In the third comparative manufacturing example, a red phosphor isobtained by applying a similar manufacturing method to those of thefirst and second manufacturing examples to 17.4 mass % of an aluminumnitride power, 44.4 mass % of an α-type silicon nitride powder, 20.1mass % of a silicon oxide powder, 20.1 mass % of a calcium nitridepowder and 3.1 mass % of a europium nitride powder. The powder of thered phosphor obtained as described above has a crystal structure where aCaAlSiN₃ phase with a structure of CaAlSiN₃ crystal is a principalphase. It is to be noted that the crystal structure was confirmed bypowder X-ray diffraction (XRD) measurement using a Cu-Kα ray. Further,when the red phosphor powder was irradiated with light with a wavelengthof 450 nm, output of red fluorescent light was confirmed.

Fluorescent properties of the red phosphor obtained by the thirdcomparative manufacturing example will be described with reference toFIG. 14. FIG. 14 is a graph showing properties of the red phosphorobtained by the third comparative manufacturing example. The graph shownin FIG. 14 is a graph showing an optical absorption spectrum of the redphosphor, where a horizontal axis indicates a wavelength (nm) and avertical axis indicates an optical absorption rate (%). It is to benoted that the graph shown in FIG. 14 is obtained such that ameasurement cell having a depth of 5 mm and a diameter of 15 mm isfilled with the powdery red phosphor, obtained by the third comparativemanufacturing example, as densely as possible by natural dropping andtapping, and this cell filled with the red phosphor is measured by ameasurement system provided with a spectro-photometer and an integratingsphere.

As for the graph shown in FIG. 14, an absolute value of wavelengthdependency of an optical absorption rate of the red phosphor at a peakwavelength (558 nm) of the fluorescent light outputted by the yellowphosphor obtained by the aforementioned common manufacturing example isobtained, to be 0.62%/nm. Further, as for the graph shown in FIG. 14, aratio is obtained by dividing an optical absorption rate RAbs(λl) of thered phosphor at the aforementioned wavelength λl by an opticalabsorption rate RAbs(λs) of the red phosphor at the aforementionedwavelength λs, to be RAbs(λl)/RAbs(λs)=0.19.

The red phosphor obtained by the third comparative manufacturing examplehas a structure of CaAlSiN₃ crystal as do the red phosphors obtained bythe first manufacturing example and the second manufacturing example.However, an absolute value of wavelength dependency of an opticalabsorption rate of the red phosphor at a peak wavelength (558 nm) of thefluorescent light outputted by the yellow phosphor is not less than0.6%/nm, and RAbs(λl)/RAbs(λs) is smaller than 0.21. That is, the redphosphor does not satisfy the aforementioned conditions for effectivelyimproving the color rendering properties of the light emitting device,and is thus difficult to apply to the light emitting device that outputswarm-color light, for example.

The relation between a value of b in the composition formula of(Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b) of the red phosphor andproperties of the red phosphor will be described with reference to FIG.15. FIG. 15 includes graphs showing the relation between the value of band the properties of the red phosphor. FIG. 15A is a graph showing therelation between the value of b set for a horizontal axis and wavelengthdependency set for a vertical axis, the wavelength dependency being thatof an optical absorption rate of the red phosphor at a peak wavelengthof the fluorescent light outputted by the yellow phosphor, and FIG. 15Bis a graph showing the relation between the value of b set for ahorizontal axis and RAbs(λl)/RAbs(λs) set for a vertical axis. Further,the graphs shown in FIG. 15 are obtained based on the properties of thered phosphors obtained by the first manufacturing example and the secondmanufacturing example and the properties of the red phosphor obtained bythe third comparative manufacturing example.

As shown in FIG. 15A, when the value of b is made larger than 0.4, thewavelength dependency of the optical absorption rate of the red phosphorat a peak wavelength of the fluorescent light emitted by the yellowphosphor abruptly increases. Further, as shown in FIG. 15B, when thevalue of b is made larger than 0.4, the ratio (RAbs(λl)/RAbs(λs)) of therespective optical absorption rates of the red phosphor in the foregoingwavelengths λs and λl abruptly decreases.

Therefore, the color rendering properties of the light emitting devicecan be effectively improved by setting the value of b to not less than 0and not more than 0.4 (preferably not more than 0.33, more preferablynot more than 0.3), to make small the wavelength dependency of theoptical absorption rate of the red phosphor in the fluorescent lightregion of the yellow phosphor.

The red phosphor with a composition formula of(Ca_(1-c)Eu_(c)AlSiN₃)_(1-b)(Si₂N₂O)_(b) can dissolve oxygen to be asolid solution while keeping the crystal structure to be the structureof CaAlSiN₃. When the value of b increases and the solid solution amountof oxygen increases, the optical absorption properties change, to allowan increase in wavelength dependency of the optical absorption rate inthe fluorescent light region of the yellow phosphor described above.Therefore, the wavelength dependency of the optical absorption rate ofthe red phosphor in the fluorescent light region of the yellow phosphorcan be reduced by making the value of b in the above composition formulasmall.

<Transformation, Etc.>

[1] Any light source is applicable so long as it emits theaforementioned blue light. However, from the viewpoint of light emissionefficiency, it is preferable to apply a light source that emits lightwith a peak wavelength of not shorter than 420 nm and not longer than480 nm. Further, from the viewpoint of making excitation efficiency ofthe phosphor high and making the values of Ra and R9 of the lightemitting device high (improving the color rendering properties), it isparticularly preferably to apply a light source that emits light with apeak wavelength of not shorter than 440 nm and not longer than 470 nm,and further a light source that emits light with a peak wavelength ofnot shorter than 455 nm.

[2] Although the YAG phosphor added with Ce as the activator has beenillustrated as the yellow phosphor, a phosphor other than this may beapplied. However, the YAG phosphor added with Ce as the activator canoutput yellow fluorescent light with high efficiency. Hence it ispreferable to apply the YAG phosphor added with Ce as the activator tothe yellow phosphor. In particular, a phosphor represented by acomposition formula of (Y_(1-d)Gd_(d))_(3-e)(Al_(1-f)Ga_(f))₅O₁₂Ce_(e)(0≦d≦1, 0≦e≦0.2, 0≦f≦1) is preferable since its fluorescent efficiencyis high and its fluorescence spectrum can be suitable for theaforementioned light emitting device. It is to be noted that, when avalue of d is made large, a wavelength of fluorescent light outputted bythe phosphor can be made long. Further, when a value off is made large,the wavelength of the fluorescent light outputted by the phosphor can bemade short. On the other hand, when the value of d is made larger than0.8, the emission efficiency of the phosphor can abruptly decrease.

[3] Although the CaAlSiN₃ phosphor added with Eu as the activator hasbeen illustrated as the red phosphor, a phosphor (e.g., nitride phosphoror oxynitride phosphor) other than this may be applied. However, theCaAlSiN₃ phosphor added with Eu as the activator is high in fluorescentefficiency and excellent in stability of temperature properties and thelike, as well as being small in wavelength dependency of the opticalabsorption rate in the fluorescent light region of the yellow phosphor(especially, the YAG phosphor added with Ce as the activator), asdescribed above. Hence it is preferable to apply the CaAlSiN₃ phosphoradded with Eu as the activator to the red phosphor.

[4] The case has been illustrated where the present invention is appliedto the light emitting device including: the light source that emits bluelight; the yellow phosphor that absorbs the blue light emitted by thelight source and outputs yellow fluorescent light having a longerwavelength than the blue light; and the red phosphor that absorbs theblue light emitted by the light source and outputs red fluorescent lighthaving a longer wavelength than yellow, but the present invention isapplicable to a light emitting device with another structure. Inparticular, it is applicable to a light emitting device at leastincluding: a light source that emits light; a first phosphor thatabsorbs the light emitted by the light source and outputs fluorescentlight whose wavelength is longer than that of the light emitted by thelight source; and a second phosphor that absorbs the light emitted bythe light source and outputs fluorescent light whose wavelength islonger than that of the fluorescent light emitted by the first phosphor.

More specifically, the present invention may be applied to a lightemitting device including: a light source that emits blue light; a greenphosphor that absorbs the blue light emitted by the light source andoutputs green fluorescent light having a longer wavelength than the bluelight; and a red phosphor that absorbs the blue light emitted by thelight source and outputs red fluorescent light having a longerwavelength than green. It is to be noted that the light emitted by thelight source is not restricted to visible light, but may be ultravioletlight or the like. Further, the present invention may be applied to alight emitting device including three or more phosphors.

INDUSTRIAL APPLICABILITY

The light emitting device of the present invention can be suitably usedfor light emitting devices such as LEDs which are applied to a varietyof illumination devices such as household illumination, medicalillumination and vehicle light tools.

EXPLANATION OF REFERENCES

-   -   1: LIGHT EMITTING DEVICE    -   2: LIGHT SOURCE    -   3: SUBSTRATE    -   4: FRAME    -   5: MOLD PORTION    -   50: TRANSLUCENT RESIN    -   51: YELLOW PHOSPHOR    -   52: RED PHOSPHOR    -   6: ADHESIVE    -   7: WIRE

What is claimed:
 1. A light emitting device comprising: a LD (LaserDiode) light source that emits light having a maximum intensity at apredetermined wavelength; a first phosphor that absorbs the lightemitted by the light source and outputs fluorescent light having amaximum intensity at a first wavelength which is longer than thepredetermined wavelength; and a second phosphor that absorbs the lightemitted by the light source and outputs fluorescent light having amaximum intensity at a second wavelength which is longer than the firstwavelength.
 2. The light emitting device according to claim 1, whereinthe predetermined wavelength is not shorter than 420 nm and not longerthan 480 nm.
 3. The light emitting device according to claim 1, whereinthe first wavelength is not shorter than 500 nm and not longer than 580nm, and the second wavelength is not shorter than 600 nm and not longerthan 680 nm.
 4. The light emitting device according to claim 2, whereinthe first phosphor is a phosphor added with Ce as an activator.
 5. Thelight emitting device according to claim 4, wherein the first phosphoris represented by a composition formula of Y₃Al₅O₁₂ including substancesobtained by replacing part or all of Y, Al and O of the compositionformula with predetermined elements.
 6. The light emitting deviceaccording to claim 2, wherein the second phosphor is a phosphor addedwith Eu as an activator.
 7. The light emitting device according to claim6, wherein the second phosphor is represented by a composition formulaof CaAlSiN₃ including substances obtained by replacing part or all ofCa, Al, Si and N of the composition formula with predetermined elements.8. The light emitting device according to claim 3, wherein the firstphosphor is a phosphor added with Ce as an activator.
 9. The lightemitting device according to claim 8, wherein the first phosphor isrepresented by a composition formula of Y₃Al₅O₁₂ including substancesobtained by replacing part or all of Y, Al and O of the compositionformula with predetermined elements.
 10. The light emitting deviceaccording to claim 3, wherein the second phosphor is a phosphor addedwith Eu as an activator.
 11. The light emitting device according toclaim 10, wherein the second phosphor is represented by a compositionformula of CaAlSiN₃ including substances obtained by replacing part orall of Ca, Al, Si and N of the composition formula with predeterminedelements.